7-(r)-aminotriazolopyrimidines, the production thereof and use of the same for combatting phytopathogenic fungi

ABSTRACT

The invention relates to 7-(R) aminotriazolopyrimidines of formula (I), in which the substituents and index have the following definitions: R 1  represents hydrogen or methyl; R 2  represents methyl; R 3  represents C 2 -C 10  alkyl, C 1 -C 4  alkoxymethyl, or C 3 -C 10  cycloalkyl; R 4  represents halogen, C 1 -C 4  alkyl, C 1 -C 4  haloalkyl or C 1 -C 4  alkoxy; n represents a number between 1 and 5; Y represents halogen, cyano, C 1 -C 4  alkyl or C 1 -C 4  alkoxy; whereby * is a chirality centre with an R-configuration. The invention also relates to a method for producing said compounds, to agents containing the compounds and to the use thereof for combating harmful fungi.

[0001] The invention relates to 7-(R)-aminotriazolopyrimidines of theformula I

[0002] where the substituents and the index are as defined below:

[0003] R¹ is hydrogen or methyl;

[0004] R² is methyl;

[0005] R³ is C₂-C₁₀-alkyl, C₁-C₄-alkoxymethyl, C₃-C₁₀-cycloalkyl;

[0006] R⁴ is halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl or C₁-C₄-alkoxy;

[0007] n is a number from 1 to 5;

[0008] Y is halogen, cyano, C₁-C₄-alkyl or C₁-C₄-alkoxy;

[0009] where * is a center of chirality in the R configuration.

[0010] Furthermore, the invention relates to a process for preparing thecompounds of the formula I, to compositions for controllingphytopathogenic fungi, which compositions comprise the compounds I, andto the use of the compounds I for controlling phytopathogenic fungi.

[0011] WO-A 98/46607 discloses racemic5-chloro-7-amino-6-(2,4,6-trifluorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidines.Furthermore, on page 7, paragraphs 1 and 2, of WO-A 98/46607, it ismentioned quite generally that, in the case of compounds having a chiralamine moiety, the respective S-enantiomers would in each case haveparticularly interesting fungicidal properties.

[0012] WO-A 98/46608 discloses racemic5-halo-7-(fluoroalkyl)amino-6-phenyl-1,2,4-triazolo[1,5-a]pyrimidines,where the α-C-atom of the 7-(fluoroalkyl)amino moiety is chiral andcarries a CF₃ group. In this publication, it is taught that therespective S-enantiomers would in each case have particularlyinteresting fungicidal properties.

[0013] It is an object of the present invention to provide compoundshaving improved activity and/or a broader activity spectrum.

[0014] Surprisingly, we have found that this object is achieved bycompounds carrying a R-configured halogen-free amino radical in the7-position.

[0015] The meanings listed above are collective terms for individualenumerations of the individual group members. All carbon chains can bestraight-chain or branched. Halogenated substituents preferably carry 1to 5 identical or different halogen atoms.

[0016] In the definitions of the symbols given in the formulae above,collective terms are used which, in general, represent the followingsubstituents:

[0017] halogen: fluorine, chlorine, bromine and iodine;

[0018] alkyl: saturated straight-chain or branched hydrocarbon radicalshaving 1 to 4, 6, 8 or 10 carbon atoms, for example C₁-C₆-alkyl, such asmethyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl,2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl,3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl,1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl,3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl,3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl,1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and1-ethyl-2-methylpropyl;

[0019] alkoxy: straight-chain or branched alkyl groups having 1 to 4carbon atoms (as mentioned above) which are attached to the skeleton viaan oxygen atom (—O—);

[0020] alkenyl: unsaturated straight-chain or branched hydrocarbonradicals having 2 to 4, 6, 8 or 10 carbon atoms and a double bond in anyposition, for example C₂-C₆-alkenyl, such as ethenyl, 1-propenyl,2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl,1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl,2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl,1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl,1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl,1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl,1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl,1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl,1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl,1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl,4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl,3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl,2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl,1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl,4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl,1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl,1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl,2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl,2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl,1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl,2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl,1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl,1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;

[0021] alkynyl: straight-chain or branched hydrocarbon groups having 2to 4, 6, 8 or 10 carbon atoms and a triple bond in any position, forexample C₂-C₆-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl,1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl,2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl,1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl,1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl,3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl,1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl,2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl,4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1,1-dimethyl-2-butynyl,1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl,3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl,2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;

[0022] cycloalkyl: monocyclic saturated hydrocarbon groups having 3 to10 carbon ring members, for example C₃-C₈-cycloalkyl, such ascyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl andcyclooctyl.

[0023] The compounds I can preferably be prepared by reacting a7-halotriazolopyrimidine of the formula II in which the substituents R⁴and Y and the index n are as defined in claim 1 with (R)-configuredamines of the formula III.

[0024] The reaction of the compound II with (R)-configured amines of theformula III is carried out, for example, in an inert solvent or diluent,such as a chlorinated hydrocarbon (in particular dichloromethane ortrichloromethane), acetone, acetonitrile, dimethyl sulfoxide,dimethylformamide, N-methylpyrrolidone, an aromatic hydrocarbon (inparticular toluene or chlorobenzene) or an ether (in particulartetrahydrofuran, dimethoxyethane or dioxane).

[0025] In general, the reaction is carried out using a base (for examplesodium carbonate, potassium carbonate, sodium hydroxide, potassiumhydroxide, sodium hydride, potassium hydride or, in particular, atertiary amine). Tertiary amines such as triethylamine,ethyldiisopropylamine or diazabicycloundecene have been found to beparticularly suitable. The bases are generally employed in equimolaramounts or in excess. Moreover, it may be advantageous to add acatalytic amount of a crown ether (for example 18-crown-6 or15-crown-5).

[0026] The reaction temperature is generally in the range from 0 to 100°C., preferably from 10 to 35° C. The reaction can, for example, becarried out at room temperature.

[0027] To isolate and purify the compounds according to the invention,it is possible to use customary methods such as extraction,chromatography or recrystallization.

[0028] The 7-halotriazolopyrimidines II required for preparing thecompounds I are known from the literature or can be prepared by methodsknown from the literature [cf. WO-A 98/46607; EP-A 550 113]. They areusually prepared by reacting 3-amino-1,2,4-triazole with 2-phenylmalonicesters or 2-phenylacetic esters of the formula IV

[0029] in which R⁴ and the index n are as defined for formula I and R isC₁-C₄-alkyl. In this manner, it is possible, starting from2-phenylmalonic esters (IVa) or diketones (IVb), to obtain5,7-dihydroxy-6-phenyltriazolopyrimidines and5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines, respectively. If theeasily accessible 2-phenylacetoacetic esters (IVb where R═CH₃) are used,5-methyl-7-hydroxy-6-phenyltriazolopyrimidines are obtained [cf. Chem.Pharm. Bull. 9 (1961), 801]. The preparation of the starting materialsIV is described in EP-A 10 02 788.

[0030] The resulting 5,7-dihydroxy-6-phenyltriazolopyrimidines and5-alkyl-7-hydroxy-6-phenyltriazolopyrimidines are reacted withhalogenating agents to give the 7-halotriazolopyrimidines of the formulaII. Preference is given to using chlorinating or brominating agents,such as phosphorus oxybromide, phosphorus oxychloride, thionyl chloride,thionyl bromide or sulfuryl chloride. The reaction can be carried out inthe absence or presence of a solvent. Customary reaction temperaturesare from 0 to 150° C., preferably from 80 to 125° C.

[0031] It is furthermore possible to prepare compounds I in which Y isalkyl by the method described in U.S. Pat. No. 5,994,360—starting from5,7-dichloro-6-phenyltriazolopyrimidines, by chlorine/amine exchange inthe 7-position and substitution of the chorine by a malonic acidradical, followed by decarboxylation.

[0032] Compounds I in which Y is methoxy can be prepared advantageouslyby the process described in WO-A 99/41255—starting from5,7-dichloro-6-phenyltriazolopyrimidines, by chlorine/amine exchange inthe 7-position and substitution of the chlorine by methoxide.

[0033] R-configured amines III can be prepared advantageously by theroute shown in scheme 1 using (R)-3,3-dimethylbut-2-amine (R-DMBA) as anexample.

[0034] The above synthesis uses racemic 3,3-dimethylbut-2-amine(rac-DMBA), which is obtainable as described in J. Am. Chem. Soc.,1939(61), p. 3500 and J. Am. Chem. Soc., 1941(63), p. 3135, as startingmaterial. Resolution of the racemate is carried out by the processdescribed in WO-A 95/08636 and WO-A 97/10201. This process involves thefollowing steps:

[0035] 1) racemic 3,3-dimethylbut-2-ylamine is enantioselectivelyacylated in the presence of a hydrolase, using an ester whose acidcomponent carries a fluorine, nitrogen, oxygen or sulfur atom in thevicinity of the carbonyl carbon,

[0036] 2) the mixture of (S)-3,3-dimethylbut-2-ylamine (S-DMBA) andacylated (R)-3,3-dimethylbut-2-ylamine (R-DMBamide) is then separatedand

[0037] 3) the acylated (R)-3,3-dimethylbut-2-ylamine is subjected toamide cleavage.

[0038] The publications WO-A 95/08636 and WO-A 97/10201 give a specificlist of the esters and hydrolases which are particularly suitable forracemate resolution, so that an explicit illustration can be dispensedwith here.

[0039] The hydrolases used are preferably proteases and in particularlipases. Particularly suitable are lipases from Pseudomonas, for exampleAmano P, or the lipase from Pseudomonas spec. DSM 8246. Otherparticularly suitable hydrolases are the enzymes available from NovoNordisk (Enzyme Toolbox), in particular the lipases SP 523, SP 524, SP525, SP 526 and Novozym® 435.

[0040] The enzyme can be used in native or immobilized form.

[0041] Amines of the formula III are either commercially available orcan be obtained by optical resolution of the racemate as illustrated inscheme 1.

[0042] Preference is given to compounds I in which R¹ is hydrogen ormethyl, in particular hydrogen.

[0043] Moreover, preference is given to compounds I in which R² ismethyl.

[0044] In addition, preference is also given to compounds of the formulaIA:

[0045] In the formula IA, R¹, R³ and (R⁴)_(n) are as defined for formulaI.

[0046] Likewise, preference is given to compounds I and IA in which R³is ethyl, isopropyl or tert-butyl, in particular tert-butyl.

[0047] Preference is given to compounds of the formula I in which n is 2or 3, in particular 3.

[0048] The substituents and the index n in the formula I are preferablyas defined below:

[0049] R⁴ is fluorine, chlorine, methyl or methoxy, in particularfluorine;

[0050] n is the number 2 or 3, in particular the number 3;

[0051] Y is fluorine, chlorine, bromine, methyl or methoxy, inparticular chlorine.

[0052] With respect to (R⁴)_(n), particular preference is given to thefollowing combinations of substituents:

[0053] 2,6-difluoro;

[0054] 2-chloro, 6-fluoro;

[0055] 2,6-dichloro;

[0056] 2-methyl-4-fluoro;

[0057] 2-methyl-6-fluoro;

[0058] 2,4,6-trifluoro;

[0059] 2,6-difluoro-4-methyl; 2,6-difluoro-4-methoxy;

[0060] pentafluoro.

[0061] Particular preference is given to the compound (R)-5-chloro-7-(3,3-dimethylbut-2-yl)amino-6-(2,4,6-trifluoro-phenyl)-1,2,4-triazolo[1,5-a]pyrimidine.

[0062] In particular with a view to their use, preference is given tothe compounds I compiled in the tables below. Moreover, the groupsmentioned for a substituent in the tables are on their own,independently of the combination in which they are mentioned, aparticularly preferred embodiment of the substituent in question.

[0063] Table 1

[0064] Compounds of the formula IA in which R¹ is hydrogen, R³ is ethyland the combination of the radicals (R⁴)_(n) for a compound correspondsin each case to one row of Table A

[0065] Table 2

[0066] Compounds of the formula IA in which R¹ is hydrogen, R³ isisopropyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0067] Table 3

[0068] Compounds of the formula IA in which R¹ is hydrogen, R³ istert-butyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0069] Table 4

[0070] Compounds of the formula IA in which R¹ is hydrogen, R³ isn-propyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0071] Table 5

[0072] Compounds of the formula IA in which R¹ is hydrogen, R³ isn-butyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0073] Table 6

[0074] Compounds of the formula IA in which R¹ is hydrogen, R³ isn-pentyl and the combination of the radicals (R⁴ )_(n) for a compoundcorresponds in each case to one row of Table A

[0075] Table 7

[0076] Compounds of the formula IA in which R¹ is hydrogen, R³ isn-hexyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0077] Table 8

[0078] Compounds of the formula IA in which R¹ is hydrogen, R³ isn-heptyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0079] Table 9

[0080] Compounds of the formula IA in which R¹ is hydrogen, R³ isn-octyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0081] Table 10

[0082] Compounds of the formula IA in which R¹ is hydrogen, R³ isn-nonyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0083] Table 11

[0084] Compounds of the formula IA in which R¹ is hydrogen, R³ isisobutyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0085] Table 12

[0086] Compounds of the formula IA in which R¹ is hydrogen, R³ iscyclopropyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0087] Table 13

[0088] Compounds of the formula IA in which R¹ is hydrogen, R³ iscyclohexyl and the combination of the radicals (R⁴)_(n) for a compoundcorresponds in each case to one row of Table A

[0089] Table 14

[0090] Compounds of the formula IA in which R¹ is hydrogen, R³ ismethoxymethyl and the combination of the radicals (R⁴)_(n) for acompound corresponds in each case to one row of Table A

[0091] Table 15

[0092] Compounds of the formula IA in which R¹ is methyl, R³ is ethyland the combination of the radicals (R⁴)_(n) for a compound correspondsin each case to one row of Table A

[0093] Table 16

[0094] Compounds of the formula IA in which R¹ is methyl, R³ is n-hexyland the combination of the radicals (R⁴)_(n) for a compound correspondsin each case to one row of Table A TABLE A No. (R⁴)_(n) A-1 2-Cl-6-F A-22,6-F₂ A-3 2,6-Cl₂ A-4 2-CH₃-6-F A-5 2,4,6-F₃ A-6 2,6-F₂-4-OCH₃ A-7 F₅A-8 2-CH₃-4-F A-9 2-CF₃ A-10 2-OCH₃-6-F A-11 2-OCH₃-4,6-F₂

[0095] The novel compounds I have excellent activity against a broadspectrum of phytopathogenic fungi, especially from the classes ofAscomycetes and Basidiomycetes, and they can be employed as foliar- andsoil-acting fungicides. Some of them have remarkably high systemicmobility and activity after soil application and in particular alsoafter foliar application.

[0096] They are especially important for controlling a large number offungi in a variety of crop plants such as wheat, rye, barley, oats,rice, corn, grass, bananas, cotton, soy, coffee, sugar cane, grapevines,fruit species, ornamentals and vegetable species such as cucumbers,beans, tomatoes, potatoes and cucurbits, and also in the seeds of theseplants.

[0097] Specifically, they are suitable for controlling the followingplant diseases:

[0098] Alternaria species, Podosphaera species, Sclerotinia species,Physalospora canker in vegetables and fruit,

[0099]Botrytis cinerea (gray mold) in strawberries, vegetables,ornamentals and grapevines,

[0100]Corynespora cassiicola in cucumbers,

[0101] Colletotrichum species in fruit and vegetables,

[0102]Diplocarpon rosae in roses,

[0103]Elsinoe fawcetti and Diaporthe citri in citrus fruits,

[0104] Sphaerotheca species in cucurbits, strawberries and roses,

[0105] Cercospora species in groundnuts, sugar beet and aubergines,

[0106]Erysiphe cichoracearum in cucurbits,

[0107]Leveillula taurica in peppers, tomatoes and aubergines,

[0108] Mycosphaerella species in apples and Japanese apricot,

[0109]Phyllactinia kakicola, Gloesporium kaki, in Japanese apricot,

[0110]Gymnosporangium yamadae, Leptothyrium pomi, Podosphaeraleucotricha and Gloedes pomigena in apples,

[0111]Cladosporium carpophilum in pears and Japanese apricot,

[0112] Phomopsis species in pears,

[0113] Phytophthora species in citrus fruits, potatoes, onions, inparticular Phytophthora infestans in potatoes and tomatoes,

[0114]Blumeria graminis (powdery mildew) in cereals,

[0115] Fusarium and Verticillium species in a variety of plants,

[0116]Glomerella cingulata in tea,

[0117] Drechslera and Bipolaris species in cereals and rice,

[0118] Mycosphaerella species in bananas and groundnuts,

[0119]Plasmopara viticola in grapevines,

[0120] Personospora species in onions, spinach and chrysanthemums,

[0121]Phaeoisariopsis vitis and Sphaceloma ampelina in grapefruits,

[0122]Pseudocercosporella herpotrichoides in wheat and barley,

[0123] Pseudoperonospora species in hops and cucumbers,

[0124] Puccinia species and Typhula species in cereals and lawns,

[0125]Pyricularia oryzae in rice,

[0126] Rhizoctonia species in cotton, rice and lawns,

[0127]Stagonospora nodorum and Septoria tritici in wheat,

[0128]Uncinula necator in gravevines,

[0129] Ustilago species in cereals and sugar cane and

[0130] Venturia species (scab) in apples and pears.

[0131] The compounds I are also suitable for controlling harmful fungisuch as Paecilomyces variotii in the protection of materials (forexample wood, paper, paint dispersions, fibers or tissues) and in theprotection of stored products.

[0132] The compounds I are employed by treating the fungi or the plants,seeds, materials or the soil to be protected against fungal attack witha fungicidally effective amount of the active compounds. The applicationmay be carried out before or after the infection of the materials,plants or seeds by the fungi.

[0133] The fungicidal compositions generally comprise from 0.1 to 95,preferably from 0.5 to 90, % by weight of active compound.

[0134] For use in crop protection, the application rates are, dependingon the kind of effect desired, from 0.01 to 2.0 kg of active compoundper ha.

[0135] The treatment of seeds generally requires active compoundquantities of from 0.001 to 0.1 g, preferably from 0.01 to 0.05 g, perkilogram of seed.

[0136] For use in the protection of materials or stored products, theactive compound application rate depends on the kind of application areaand desired effect. Customary application rates in the protection ofmaterials are, for example, from 0.001 g to 2 kg, preferably from 0.005g to 1 kg, of active compound per cubic meter of treated material.

[0137] The compounds I can be converted into the customary formulations,e.g. solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The use form depends on the specific intended use; in anycase, it should ensure fine and uniform distribution of the compoundaccording to the invention.

[0138] The formulations are prepared in a known manner, e.g. byextending the active compound with solvents and/or carriers, if desiredusing emulsifiers and dispersants, it also being possible to use otherorganic solvents as auxiliary solvents if the diluent used is water.Suitable auxiliaries for this purpose are essentially: solvents such asaromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes),paraffins (e.g. mineral oil fractions), alcohols (e.g. methanol,butanol), ketones (e.g. cyclohexanone), amines (e.g. ethanolamine,dimethylformamide) and water; carriers such as ground natural minerals(e.g. kaolins, clays, talc, chalk) and ground synthetic minerals (e.g.finely divided silica, silicates); emulsifiers such as nonionic andanionic emulsifiers (e.g. polyoxyethylene fatty alcohol ethers,alkylsulfonates and arylsulfonates), and dispersants such aslignosulfite waste liquors and methylcellulose.

[0139] Suitable surfactants are the alkali metal, alkaline earth metal,and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid,phenolsulfonic acid, dibutylnaphthalenesulfonic acid,alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcoholsulfates and fatty acids and alkali metal salts and alkaline earth metalsalts thereof, salts of sulfated fatty alcohol glycol ethers,condensation products of sulfonated naphthalene and naphthalenederivatives with formaldehyde, condensation products of naphthalene orof naphthalene sulfonic acid with phenol and formaldehyde,polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol,octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenylpolyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol,fatty alcohol ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignosulfite wasteliquors and methylcellulose.

[0140] Suitable for preparing directly sprayable solutions, emulsions,pastes or oil dispersions are petroleum fractions having medium to highboiling points, such as kerosene or diesel fuel, furthermore coal-taroils and oils of plant or animal origin, aliphatic, cyclic and aromatichydrocarbons, for example benzene, toluene, xylene, paraffin,tetrahydronaphthalene, alkylated naphthalene or derivatives thereof,methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride,cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polarsolvents, for example dimethylformamide, dimethyl sulfoxide,N-methylpyrrolidone, and water.

[0141] Powders, compositions for broadcasting and dusts can be preparedby mixing or joint grinding of the active substances with a solidcarrier.

[0142] Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers. Solid carriers are, for example, mineral earths, such assilica gel, silicas, silicates, talc, kaolin, attaclay, limestone, lime,chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as ammonium sulfate, ammonium phosphate, ammoniumnitrate, ureas and products of vegetable origin, such as cereal meal,tree bark meal, wood meal and nutshell meal, cellulose powders and othersolid carriers.

[0143] The formulations generally comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active compound. The activecompounds are employed in a purity of from 90% to 100%, preferably from95% to 100% (according to the NMR spectrum).

[0144] Examples of formulations are:

[0145] I. 5 parts by weight of a compound according to the invention areintimately mixed with 95 parts by weight of finely divided kaolin. Thisaffords a dust comprising 5% by weight of the active compound.

[0146] II. 30 parts by weight of a compound according to the inventionare intimately mixed with a mixture of 92 parts by weight of pulverulentsilica gel and 8 parts by weight of paraffin oil which have been sprayedonto the surface of this silica gel. This affords an active compoundpreparation having good adhesive properties (active compound content 23%by weight).

[0147] III. 10 parts by weight of a compound according to the inventionare dissolved in a mixture comprising 90 parts by weight of xylene, 6parts by weight of the addition product of 8 to 10 mol of ethylene oxideto 1 mol of oleic acid N-monoethanolamide, 2 parts by weight of thecalcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of theaddition product of 40 mol of ethylene oxide to 1 mol of castor oil(active compound content 9% by weight).

[0148] IV. 20 parts by weight of a compound according to the inventionare dissolved in a mixture comprising 60 parts by weight ofcyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight ofthe addition product of 7 mol of ethylene oxide to 1 mol ofisooctylphenol and 5 parts by weight of the addition product of 40 molof ethylene oxide to 1 mol of castor oil (active compound content 16% byweight).

[0149] V. 80 parts by weight of a compound according to the inventionare intimately mixed with 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of thesodium salt of a lignosulfonic acid from a sulfite waste liquor and 7parts by weight of pulverulent silica gel, well mixed and ground in ahammer mill (active compound content 80% by weight).

[0150] VI. 90 parts by weight of a compound according to the inventionare mixed with 10 parts by weight of N-methyl-α-pyrrolidone, affording asolution which is suitable for use in the form of very small drops(active compound content 90% by weight).

[0151] VII. 20 parts by weight of a compound according to the inventionare dissolved in a mixture comprising 40 parts by weight ofcyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight ofthe addition product of 7 mol of ethylene oxide to 1 mol ofisooctylphenol and 10 parts by weight of the addition product of 40 molof ethylene oxide to 1 mol of castor oil. The solution is poured onto100,000 parts by weight of water and finely dispersed therein, affordingan aqueous dispersion comprising 0.02% by weight of active compound.

[0152] VIII. 20 parts by weight of a compound according to the inventionare intimately mixed with 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodiumsalt of a lignosulfonic acid from a sulfite waste liquor and 60 parts byweight of pulverulent silica gel, and ground in a hammer mill. Themixture is finely dispersed in 20,000 parts by weight of water,affording a spray liquor comprising 0.1% by weight of active compound.

[0153] IX. 10 parts by weight of the compound according to the inventionare dissolved in 63 parts by weight of cyclohexanone, 27 parts by weightof dispersant (for example a mixture of 50 parts by weight of theaddition product of 7 mol of ethylene oxide to 1 mol of isooctylphenoland 50 parts by weight of the addition product of 40 mol of ethyleneoxide to 1 mol of castor oil). The stock solution is then diluted to thedesired concentration by dispersion in water, for example to aconcentration in the range from 1 to 100 ppm.

[0154] The active compounds can be applied as such, in the form of theirformulations or in the application forms prepared therefrom, for examplein the form of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dusts, compositions forbroadcasting, or granules, by spraying, atomizing, dusting, broadcastingor watering. The application forms depend entirely on the intended uses;in any case, they should ensure very fine dispersion of the activecompounds according to the invention.

[0155] Aqueous use forms can be prepared from emulsion concentrates,pastes or wettable powders (spray powders, oil dispersions) by additionof water. To prepare emulsions, pastes or oil dispersions, thesubstances can be homogenized in water as such or dissolved in an oil orsolvent, by means of wetting agents, tackifiers, dispersants oremulsifiers. However, concentrates comprising active compound, wettingagent, tackifier, dispersant or emulsifier and possibly solvent or oilwhich are suitable for dilution with water can also be prepared.

[0156] The active compound concentrations in the ready-to-usepreparations can be varied over a relatively wide range. In general,they are from 0.0001 to 10%. Frequently, even low amounts of the activecompound I in the ready-to-use preparation are sufficient, for example 2to 200 ppm. Preference is also given to ready-to-use preparations havingactive compound concentrations in the range from 0.01 to 1%.

[0157] It is also possible to use the active compounds with a highdegree of success in the ultra-low-volume method (ULV), it beingpossible to apply formulations comprising more than 95% by weight ofactive compound or even the active compound without additives.

[0158] Oils of various types, herbicides, fungicides, other pesticidesand bactericides can be added to the active compounds, if desired evenimmediately prior to application (tank mix). These agents can be addedto the compositions according to the invention in a weight ratio of 1:10to 10:1.

[0159] The compositions according to the invention in the use form asfungicides may also be present in combination with other activecompounds, for example with herbicides, insecticides, growth regulators,fungicides or else with fertilizers. In many cases, a mixture of thecompounds I, or of the compositions comprising them, in the use form asfungicides with other fungicides results in a broader fungicidalspectrum of activity.

[0160] The following list of fungicides in combination with which thecompounds according to the invention can be used is intended toillustrate the possible combinations, but not to impose any limitation:

[0161] sulfur, dithiocarbamates and their derivatives, such as iron(III)dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zincethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate,manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuramdisulfide, ammonia complex of zinc (N,N-ethylenebisdithiocarbamate),ammonia complex of zinc (N,N′-propylenebisdithiocarbamate), zinc(N,N′-propylenebisdithiocarbamate),N,N′-polypropylenebis(thiocarbamoyl)disulfide;

[0162] nitro derivatives, such as dinitro-(1-methylheptyl)phenylcrotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate,2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, diisopropyl5-nitroisophthalate;

[0163] heterocyclic substances, such as 2-heptadecyl-2-imidazolineacetate, 2-chloro-N-(4′-chlorobiphenyl-2-yl)nicotinamide,2,4-dichloro-6-(o-chloroanilino)-s-triazine, O,O-diethylphthalimidophosphonothioate,5-amino-1-[bis(dimethylamino)phosphinyl]-3-phenyl-1,2,4-triazole,2,3-dicyano-1,4-dithioanthraquinone,2-thio-1,3-dithiolo[4,5-b]quinoxaline, methyl1-(butylcarbamoyl)-2-benzimidazolecarbamate,2-methoxycarbonylaminobenzimidazole, 2-(fur-2-yl)benzimidazole,2-(thiazol-4-yl)benzimidazole,N-(1,1,2,2-tetrachloroethylthio)tetrahydrophthalimide,N-trichloromethylthiotetrahydrophthalimide,N-trichloromethylthiophthalimide,

[0164] N-dichlorofluoromethylthio-N′,N′-dimethyl-N-phenylsulfuricdiamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,2-thiocyanatomethylthiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene,4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone, pyridine2-thio-1-oxide, 8-hydroxyquinoline or its copper salt,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine,2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine 4,4-dioxide,2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,2-methylfuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxanilide,2,4,5-trimethylfuran-3-carboxanilide,N-cyclohexyl-2,5-dimethylfuran-3-carboxamide,N-cyclohexyl-N-methoxy-2,5-dimethylfuran-3-carboxamide,2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine2,2,2-trichloroethyl acetal,piperazine-1,4-diylbis-1-(2,2,2-trichloroethyl)formamide,1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,2,6-dimethyl-N-tridecylmorpholine or its salts,2,6-dimethyl-N-cyclododecylmorpholine or its salts,N-[3-(p-tert-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,N-[3-(p-tert-butylphenyl)-2-methyl-propyl]piperidine,1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-di-oxolan-2-ylethyl]-1H-1,2,4-triazole,1-[2-(2,4-dichloro-phenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole,N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N′-imidazolylurea,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanone,1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)-2-butanol,(2RS,3RS)-1-[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-ylmethyl]-1H-1,2,4-triazole,α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine,bis(p-chlorophenyl)-3-pyridinemethanol,1,2-bis(3-ethoxycarbonyl-2-thioureido)benzene,1,2-bis(3-methoxycarbonyl-2-thioureido)benzene, strobilurins, such asmethyl E-methoxyimino-[α-(o-tolyloxy)-o-tolyl]acetate, methylE-2-{2-[6-(2-cyanophenoxy)-pyridimin-4-yloxy]phenyl}-3-methoxyacrylate,methyl E-methoxyimino-[α-(2-phenoxyphenyl)]acetamide, methylE-methoxyimino-[α-(2,5-dimethylphenoxy)-o-tolyl]acetamide, methylE-2-{2-[(2-trifluoromethylpyrid-6-yl)oxymethyl]phenyl}-3-methoxyacrylate,methyl(E,E)-methoximino-{2-[1-(3-trifluoromethylphenyl)ethylidene-aminooxymethyl]phenyl}acetate,methylN-(2-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxymethyl}phenyl)-N-methoxycarbamate,

[0165] anilinopyrimidines, such asN-(4,6-dimethylpyrimidin-2-yl)aniline,N-[4-methyl-6-(1-propynyl)pyrimidin-2-yl]aniline,N-(4-methyl-6-cyclopropylpyrimidin-2-yl)aniline,

[0166] phenylpyrroles, such as4-(2,2-difluoro-1,3-benzodioxol-4-yl)pyrrole-3-carbonitrile,

[0167] cinnamamides, such as3-(4-chlorophenyl)-3-(3,4-dimethoxy-phenyl)acryloylmorpholide,3-(4-fluorophenyl)-3-(3,4-dimethoxyphenyl)acryloylmorpholide,

[0168] and a variety of fungicides, such as dodecylguanidine acetate,1-(3-bromo-6-methoxy-2-methylphenyl)-1-(2,3,4-trimethoxy-6-methylphenyl)methanone,3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutarimide,hexachlorobenzene, methylN-(2,6-dimethylphenyl)-N-(2-furoyl)-DL-alaninate,DL-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)alanine methyl ester,N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone,DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester,5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,3-(3,5-dichlorophenyl)-5-methyl-5-methoxy-methyl-1,3-oxazolidine-2,4-dione,3-(3,5-dichlorophenyl)-1-isopropylcarbamoylhydantoin,N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,1-[2-(2,4-dichlorophenyl)pentyl]-1H-1,2,4-triazole,2,4-difluoro-α-(1H-1,2,4-triazolyl-1-methyl)benzohydryl alcohol,N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro-2-aminopyridine,1-((bis(4-fluorophenyl)methylsilyl)methyl)-1H-1,2,4-triazole,N,N-dimethyl-5-chloro-2-cyano-4-p-tolylimidazole-1-sulfonamide,3,5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide.

[0169] Synthesis of the Precursor

[0170] Preparation of (R)-3,3-dimethylbut-2-ylamine (the synthesis wascarried out according to Scheme 1 on page 6 of the description)

[0171] a) Resolution of the Racemate

[0172] 280 g (2.75 mol) of racemic 3,3-dimethylbut-2-ylamine wereinitially charged, cooled to about 15° C. and mixed with 187 g (1.42mol) of isopropyl methoxy acetate. 3 g of Novozym® 435 (=lipase fromCandida antarctica) were then added, and the mixture was stirred at25-30° C. for 2 days. The optical purity of the(S)-3,3-dimethylbut-2-ylamine (S-DMBA) was then 97% ee and that of theN-(3,3-dimethylbut-2-yl)-α-methoxyacetamide (R-DMBamide) formed was99.3% ee (conversion: 49.4%). The catalyst was filtered off with suctionand washed twice with in each case 30 ml of isopropanol. The combinedfiltrates were separated distillatively using a thin-film evaporator. Ata top pressure of 50 mbar and a mantel temperature of 140° C., a mixtureof isopropanol and S-DMBA having a boiling point of 45° C. distilled offvia the top. The less volatile bottom consisted of R-DMBamide andunreacted acylating agent, isopropyl methoxyacetate. This less volatilemixture was once more charged using the thin-film evaporator. This time,the mantel temperature was adjusted to 140° C. and the top pressure to35 mbar. At 60° C., the unreacted acylating agent, isopropyl methoxyacetate, distilled off via the top. The less volatile bottom consistedof pure R-DMBamide (ee: 99.3%), yield 249 g (94%).

[0173] b) Amide Cleavage and Pure Distillation:

[0174] 190 g (1.1 mol) of R-DMBamide were diluted with 100 g oftriethanolamine and, with stirring, heated at 120° C. At thistemperature, 150 g of 50% strength aqueous sodium hydroxide solution andthen 100 g of water were introduced over a period of 2 hours. The(R)-3,3-dimethylbut-2-ylamine (R-DMBA) formed distilled offazeotropically with water (top temperature: 84-86° C.). The reflux wasled through a phase separator, and the aqueous amine, which separatedoff as upper phase, was discharged. The lower phase (water) was recycledinto the reaction flask. The mixture was boiled until the toptemperature had remained above 95° C. for 6 hours. The aqueous aminethat had been separated off (water content: 45%) was mixed with 100 mlof n-hexane, and the mixture was heated to reflux. At a top temperatureof 61° C., a heteroazeotrope consisting of n-hexane and water distilledoff. At total reflux the azeotrope was led through a phase separator andthe aqueous lower phase was separated off. The upper phase was returnedto the distillation flask. Once all the water had been removedazeotropically, the top temperature increased to 69° C. Using areflux/discharge ratio of 5:1, the entrainer n-hexane was distilled off.When the temperature had reached 71° C., the reflux/discharge ratio wasincreased to 10:1, and an intermediate fraction was collected up to atop temperature of 103° C. The pure product distilled at 103° C. Thisgave 105 g (99%) of the product as a colorless liquid.

[0175]¹H-NMR (360 MHz, CDCl₃): 0.85 ppm (s, 9 H), 1.00 ppm (d, J=7 Hz, 3H), 1.25 ppm (s, wide, 2H), 2.60 ppm (q, J=7 Hz, 1 H).

[0176] Preparation of5,7-dihydroxy-6-(2,4,6-trifluorophenyl)-1,2,4-triazolo[1,5-a]pyrimidine

[0177] A mixture of 22 mmol of diethyl2-(2,4,6-trifluorophenyl)malonate, 24 mmol of triethylamine and 22 mmolof 3-amino-1,2,4-triazole was heated with stirring at 180° C. for 6hours. The reaction mixture was then cooled to 50° C., admixed with asolution of 2.2 g of sodium hydroxide in 25 ml of water and stirred for30 minutes. The aqueous phase was washed with ether and then acidifiedwith conc. hydrochloric acid. The precipitated colorless solid wasfiltered off, washed with water and diisopropyl ether and dried. Theyield of the title compound was 85% (m.p.: 200-201° C.).

[0178] Preparation of

[0179]5,7-dichloro-6-(2,4,6-trifluorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidine

[0180] 16 mmol of5,7-dihydroxy-6-(2,4,6-trifluorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidinein 20 ml of phosphorus oxychloride were heated to the boil for 4 hours.Excess phosphorus oxychloride was distilled off. The distillationresidue was cooled to room temperature and admixed with 100 ml ofdichloromethane. 125 ml of water were then added at a temperature below40° C. The organic phase was dried over sodium sulfate and the solventwas then distilled off. A colorless solid remained in the reactionvessel, with a yield of 72% (m.p.: 125-126° C.).

[0181] Synthesis of the Active Compounds

[0182] The procedures shown in the Synthesis Examples below were, withappropriate modification of the starting materials, used to obtainfurther compounds I. The resulting compounds are listed in the tablesbelow, together with physical data.

EXAMPLE 1

[0183] Preparation of(R)-5-chloro-7-(3,3-dimethylbut-2-yl)amino-6-(2,4,6-trifluoro-phenyl)-1,2,4-triazolo[1,5-a]pyrimidine

[0184] With stirring, a mixture of 1.4 mmol of(R)-3,3-dimethylbut-2-ylamine, 1.4 mmol of triethylamine and 10 ml ofdichloromethane was introduced into a mixture of 1.4 mmol of5,7-dichloro-6-(2,4,6-trifluorophenyl)-1,2,4-triazolo[1,5-a]-pyrimidinein 30 ml of dichloromethane. The reaction mixture was then stirred atroom temperature for 16 hours and finally washed with 1 N hydrochloricacid and water. The organic phase was dried over anhydrous sodiumsulfate. The solvent was distilled off under reduced pressure. The crudeproduct was purified by silica gel column chromatography. This gave thetitle compound in the form of colorless crystals in a yield of 76%(m.p.: 169-171° C.). TABLE A IA

Phys. data No. R¹ R³ (R⁴)_(n) (m.p.[° C.]) I-1 H CH₂CH₃ 2-Cl-6-F 147 I-2H CH(CH₃)₂ 2-Cl-6-F 145 I-3 H C(CH₃)₃ 2-Cl-6-F 191 I-4 H CH₂CH₃ 2,6-F₂176 I-5 H CH(CH₃)₂ 2,6-F₂ 149 I-6 H C(CH₃)₃ 2,6-F₂ 175 I-7 H CH₂CH₃2,6-Cl₂ 123 I-8 H CH(CH₃)₂ 2,6-Cl₂ 132 I-9 H C(CH₃)₃ 2,6-Cl₂ 216 I-10 HCH₂CH₃ 2-CH₃-6-F 123 I-11 H CH(CH₃)₂ 2-CH₃-6-F 116/132 I-12 H C(CH₃)₃2-CH₃-6-F 158/203 I-13 H CH₂CH₃ 2,4,6-F₃ 87 I-14 H CH(CH₃)₂ 2,4,6-F₃ 87I-15 H C(CH₃)₃ 2,4,6-F₃ 170 I-16 H CH₂CH₃ 2,6-F₂-4-OCH₃ 129 I-17 HCH(CH₃)₂ 2,6-F₂-4-OCH₃ 141 I-18 H C(CH₃)₃ 2,6-F₂-4-OCH₃ 186 I-19 HCH₂CH₃ F₅ 99 I-20 H CH(CH₃)₂ F₅ 152 I-21 H C(CH₃)₃ F₅ 109 I-22 H CH₂CH₃2-CH₃-4-F 124 I-23 H CH(CH₃)₂ 2-CH₃-4-F 123 I-24 H C(CH₃)₃ 2-CH₃-4-F 154I-25 H CH(CH₃)₂ 2-CF₃ 154 I-26 H C(CH₃)₃ 2-CF₃ 142 I-27 H (CH₂)₃CH₃2,4,6-F₃ 91 I-28 H (CH₂)₄CH₃ 2,4,6-F₃ 189 I-29 H (CH₂)₅CH₃ 2,4,6-F₃ 169I-30 H (CH₂)₆CH₃ 2,4,6-F₃ 175 I-31 H cyclohexyl 2,4,6-F₃ 145 I-32 HCH₂OCH₃ 2,4,6-F₃ 97 I-33 H CH₂CH₃ 2-CH₃-4-Cl 114 I-34 H CH(CH₃)₂2-CH₃-4-Cl 130 I-35 H C(CH₃)₃ 2-CH₃-4-Cl 159 I-36 H CH₂CH₃ 2-F-4-CH₃I-37 H CH(CH₃)₂ 2-F-4-CH₃ I-38 H C(CH₃)₃ 2-F-4-CH₃ I-39 H CH₂CH₃2-F-6-OCH₃ I-40 H CH(CH₃)₂ 2-F-6-OCH₃ I-41 H C(CH₃)₃ 2-F-6-OCH₃ I-42 HCH₂CH₃ 2-Cl 110 I-43 H CH(CH₃)₂ 2-Cl 95/112 I-44 H C(CH₃)₃ 2-Cl 152/196

[0185] Owing to the chiral 7-amino group and the hindered rotation ofthe 6-phenyl group, in the case of unsymmetrical phenyl substitution,there are in each case two diastereomers which may differ in theirphysical properties.

Use Examples

[0186] Examples of the activity against harmful fungi

[0187] The fungicidal action of the compounds of the formula I wasdemonstrated by the following experiments:

[0188] The active compounds were prepared separately or jointly as a 10%strength emulsion in a mixture of 70% by weight of cyclohexanone, 20% byweight of Nekanil® LN (Lutensol® AP6, wetting agent having emulsifyingand dispersing action based on ethoxylated alkylphenols) and 10% byweight of Wettol® EM (nonionic emulsifier based on ethoxylated castoroil) and diluted with water to the desired concentration.

[0189] General remarks for Use Examples 1 to 4

[0190] In WO-A 98/46607, some of the compounds listed below aredescribed as racemates. Furthermore, on page 7, paragraphs 1 and 2, itis emphasized that, in particular with respect to compounds having ahaloalkylamine substitution in the 7-position, preference is given tothe S enantiomers. The present compounds have a non-halogenatedalkylamine moiety in the 7-position. Analogously, here too, an increasedefficacy of the S enantiomers was to be expected. In the experimentsbelow, the R enantiomer and the S enantiomer are in each case compared.

Use Example 1

[0191] Curative Activity Against Brown Rust of Wheat caused by Pucciniarecondita

[0192] Leaves of potted wheat seedlings of the cultivar “Kanzler” weredusted with spores of brown rust (Puccinia recondita). The pots werethen placed in a chamber with high atmospheric humidity (90 to 95%) at20-22° C. for 24 hours. During this period, the spores germinated andthe germinal tubes penetrated into the leaf tissue. The following day,the infected plants were sprayed to runoff point with an aqueouspreparation of active compound which had been prepared from a stocksolution made of 10% of active compound, 85% of cyclohexanone and 5% ofemulsifier. After the spray coating had dried on, the test plants werecultivated in a greenhouse at 20-22° C. and 65-70% relative atmospherichumidity for 7 days. The extent of the rust fungus development on theleaves was then determined. % infection of the leaves after applicationof an aqueous preparation comprising . . . Active compound ppm of activecompound of Table I 250 63 16 ppm No. I.-1 (R)-amine 0 3 5 comparison(S)-amine 15 20 60 No. I.-2 (R)-amine 5 5 15 comparison (S)-amine 100100 100 I.-3 (R)-amine 20 / / comparison (S)-amine 100 / / No. I.-4(R)-amine 10 20 40 comparison (S)-amine 100 100 100 No. I.-5 (R)-amine10 10 / comparison (S)-amine 100 100 / No. I.-7 (R)-amine / / 40comparison (S)-amine / / 100 No. I.-10 (R)-amine 15 40 60 comparison(S)-amine 100 100 100 No. I.-11a (R)-amine 5 5 80 comparison (S)-amine30 60 100 No. I.-11b (R)-amine 5 20 / comparison (S)-amine 100 100 / No.I.-13 (R)-amine / 0 3 comparison (S)-amine / 3 60 No. I.-14 (R)-amine /0 0 comparison (S)-amine / 5 100 No. I.-15 (R)-amine 0 0 0 comparison(S)-amine 100 100 100 No. I.-16 (R)-amine / 0 7 comparison (S)-amine / 5100 No. I.-22 (R)-amine 3 5 30 comparison (S)-amine 100 100 100 No.I.-23 (R)-amine 0 0 3 comparison (S)-amine 100 100 100 No. I.-27(R)-amine 40 / / comparison (S)-amine 100 / / No. I.-32 (R)-amine 15 70/ comparison (S)-amine 80 100 / No. I.-42 (R)-amine 5 20 30 comparison(S)-amine 15 60 100 No. I.-44a (R)-amine 60 / / comparison (S)-amine 100/ / untreated 100

Use Example 2

[0193] Activity Against Net Blotch of Barley Caused by Pyrenophora teres

[0194] Leaves of potted barley seedlings of the cultivar “Igri” weresprayed to runoff point with an aqueous preparation of active compoundwhich had been prepared from a stock solution made of 10% of activecompound, 85% of cyclohexanone and 5% of emulsifier and were inoculated24 hours after the spray coating had dried on with an aqueous sporesuspension of Pyrenophora teres, the net blotch pathogen. The testplants were then placed in a greenhouse at 20-24° C. and 95-100%relative atmospheric humidity. After 6 days, the extent of thedevelopment of the disease was determined visually in % infection of theentire leaf area. % infection of the leaves after application of anaqueous preparation comprising . . . Active compound ppm of activecompound of Table I 250 63 16 ppm No. I.-1 (R)-amine / 0 50 comparison(S)-amine / 20 100 No. I.-5 (R)-amine / / 20 comparison (S)-amine / / 80No. I.-6 (R)-amine / 0 0 comparison (S)-amine / 5 60 No. I.-7 (R)-amine15 30 80 comparison (S)-amine 100 100 100 No. I.-8 (R)-amine 15 15 40comparison (S)-amine 100 100 100 No. I.-9 (R)-amine 0 0 0 comparison(S)-amine 100 100 100 No. I.-10 (R)-amine 3 3 / comparison (S)-amine 40100 / No. I.-11a (R)-amine 0 0 5 comparison (S)-amine 100 100 100 No.I.-11b (R)-amine 0 15 / comparison (S)-amine 100 100 / No. I.-12a(R)-amine 0 0 0 comparison (S)-amine 100 100 100 No. I.-12b (R)-amine 07 7 comparison (S)-amine 100 100 100 No. I.-13 (R)-amine / / 20comparison (S)-amine / / 60 No. I.-14 (R)-amine / / 3 comparison(S)-amine / / 40 No. I.-19 (R)-amine 30 / / comparison (S)-amine 80 / /No. I.-20 (R)-amine 0 10 30 comparison (S)-amine 7 40 100 No. I.-22(R)-amine / 0 7 comparison (S)-amine / 7 80 No. I.-23 (R)-amine / / 0comparison (S)-amine / / 60 No. I.-27 (R)-amine 0 0 3 comparison(S)-amine 7 90 100 No. I.-28 (R)-amine 20 40 90 comparison (S)-amine 100100 100 No. I.-31 (R)-amine 0 3 40 comparison (S)-amine 80 80 100 No.I.-32 (R)-amine 0 0 5 comparison (S)-amine 30 80 90 No. I.-44a (R)-amine/ 7 60 comparison (S)-amine / 30 100 untreated 100

Use Example 3

[0195] Protective Activity Against Septoria foliar blotch disease ofwheat caused by Septoria tritici

[0196] Leaves of potted wheat seedlings of the cultivar “Riband” weresprayed to runoff point with an aqueous preparation of active compoundwhich had been prepared from a stock solution made of 10% of activecompound, 85% of cyclohexanone and 5% of emulsifier. 24 hours after thespray coating had dried on, they were inoculated with an aqueous sporesuspension of Septoria tritici. The suspension contained 2.0×10⁶spores/ml. The test plants were then placed in a greenhouse at 18-22° C.and a relative atmospheric humidity of close to 100%. After 2 weeks, theextent of the development of the disease was determined visually in %infection of the entire leaf area. % infection of the leaves afterapplication of an aqueous preparation comprising . . . Active compoundppm of active compound of Table I 250 63 16 ppm No. I.-2 (R)-amine 0 0 0comparison (S)-amine 90 90 90 No. I.-4 (R)-amine 3 15 20 comparison(S)-amine 90 100 100 No. I.-5 (R)-amine 15 15 15 comparison (S)-amine100 100 100 No. I.-7 (R)-amine 15 30 70 comparison (S)-amine 90 90 90No. I.-8 (R)-amine 30 30 70 comparison (S)-amine 90 90 90 No. I.-14(R)-amine 15 15 15 comparison (S)-amine 70 70 90 No. I.-16 (R)-amine 7070 / comparison (S)-amine 90 90 / No. I.-17 (R)-amine 10 10 10comparison (S)-amine 90 90 90 No. I.-18 (R)-amine 30 / / comparison(S)-amine 80 / / No. I.-19 (R)-amine 10 10 50 comparison (S)-amine 90 9090 No. I.-20 (R)-amine 10 10 10 comparison (S)-amine 90 90 90 No. I.-25(R)-amine 0 0 0 comparison (S)-amine 100 100 100 No. I.-26 (R)-amine 0 03 comparison (S)-amine 100 100 100 No. I.-44a (R)-amine 7 7 60comparison (S)-amine 100 100 100 No. I.-44b (R)-amine 10 10 30comparison (S)-amine 80 80 80 untreated 100

Use Example 4

[0197] Activity Against Mildew of Wheat Caused by Blumeria graminisforma specialis tritici

[0198] Leaves of potted wheat seedlings of the cultivar “Kanzler” weresprayed to runoff point with an aqueous preparation of active compoundwhich had been prepared from a stock solution made of 10% of activecompound, 85% of cyclohexanone and 5% of emulsifier and were dusted 24hours after the spray coating had dried on with spores of mildew ofwheat (Blumeria graminis forma specialis tritici). The test plants werethen placed in a greenhouse at 20-24° C. and 60-90% relative atmospherichumidity. After 7 days, the extent of the mildew development wasdetermined visually in % infection of the entire leaf area. % infectionof the leaves after application of an aqueous preparation comprising . .. Active compound ppm of active compound of Table I 250 63 16 ppm No.I.-2 (R)-amine 40 40 / comparison (S)-amine 100 100 / No. I.-4 (R)-amine60 60 80 comparison (S)-amine 100 100 100 No. I.-5 (R)-amine 20 40 40comparison (S)-amine 100 100 100 No. I.-6 (R)-amine 40 50 / comparison(S)-amine 90 90 / No. I.-7 (R)-amine 60 / / comparison (S)-amine 100 / /No. I.-10 (R)-amine 15 60 / comparison (S)-amine 100 100 / No. I.-11a(R)-amine 5 7 7 comparison (S)-amine 60 60 80 No. I.-11b (R)-amine 30 30/ comparison (S)-amine 60 60 / No. I.-12a (R)-amine 7 7 7 comparison(S)-amine 100 100 100 No. I.-12b (R)-amine 60 60 60 comparison (S)-amine100 100 100 No. I.-13 (R)-amine / 40 60 comparison (S)-amine / 60 100No. I.-14 (R)-amine 20 30 30 comparison (S)-amine 80 80 100 No. I.-15(R)-amine 3 7 7 comparison (S)-amine 40 80 90 No. I.-16 (R)-amine 20 4040 comparison (S)-amine 100 100 100 No. I.-17 (R)-amine 60 60 60comparison (S)-amine 100 100 100 No. I.-19 (R)-amine 7 7 / comparison(S)-amine 30 30 / No. I.-20 (R)-amine 5 20 30 comparison (S)-amine 40 4080 No. I.-22 (R)-amine 3 3 5 comparison (S)-amine 70 70 80 No. I.-23(R)-amine 3 5 15 comparison (S)-amine 40 60 60 No. I.-24 (R)-amine 3 510 comparison (S)-amine 15 60 60 No. I.-31 (R)-amine 5 7 15 comparison(S)-amine 15 50 50 No. I.-44a (R)-amine 30 30 50 comparison (S)-amine100 100 100 untreated 100

[0199] In the above experiments, in all cases the R enantiomer showsconsiderably better activity than the S enantiomer.

We claim:
 1. A 7-(R)-aminotriazolopyrimidine of the formula I

where the substituents and the index are as defined below: R¹ ishydrogen or methyl; R² is methyl; R³ is C₂-C₁₀-alkyl,C₁-C₄-alkoxymethyl, C₃-C₁₀-cycloalkyl; R⁴ is halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl or C₁-C₄-alkoxy; n is a number from 1 to 5; Y ishalogen, cyano, C₁-C₄-alkyl or C₁-C₄-alkoxy; where * is a center ofchirality in the R configuration.
 2. A compound of the formula I asclaimed in claim 1, where R¹ is hydrogen; R³ is C₂-C₁₀-alkyl orC₃-C₁₀-cycloalkyl; and Y is chlorine.
 3. A compound of the formula I asclaimed in claim 2, where R³ is tert-butyl or isopropyl.
 4. A compoundof the formula I as claimed in any of claims 1 to 3, where (R⁴)_(n) hasthe following meaning: 2,6-difluoro; 2-chloro-6-fluoro; 2,6-dichloro;2-methyl-4-fluoro; 2-methyl-6-fluoro; 2,4,6-trifluoro;2,6-difluoro-4-methyl; 2,6-difluoro-4-methoxy; pentafluoro.
 5. A processfor preparing the compounds I as claimed in claim 1, which comprisesreacting a 7-halotriazolopyrimidine of the formula II,

in which the substituents R⁴ and Y and the index n are as defined inclaim 1, with a (R)-configured amine of the formula III

in which the substituents R¹, R² and R³ are as defined in claim
 1. 6. Aprocess as claimed in claim 5, wherein (R)-3,3-dimethylbut-2-ylamine or(R)-3-methylbut-2-ylamine is used.
 7. A process as claimed in claim 5,wherein a (R)-configured amine of the formula III is prepared by i)enantioselectively acylating, in the presence of a hydrolase, a racemicamine III with an ester whose acid component carries a fluorine,nitrogen, oxygen or sulfur atom in the vicinity of the carbonyl carbon,ii) separating the mixture of (S)-amine III and acylated (R)-amine IIIand iii) subjecting the acylated (R)-amine III to an amide cleavage. 8.A fungicidal composition, comprising solid and/or liquid carriers and afungicidally effective amount of at least one compound of the formula Ias claimed in claim
 1. 9. A method for controlling phytopathogenic fungiwhich comprises treating the fungi or the materials, plants, seeds orthe soil threatened by fungal attack with a fungicidally effectiveamount of at least one compound of the formula I as claimed in claim 1.